On the origin of optical rotation changes during the κ-carrageenan disorder-to-order transition
| dc.citation.volume | 333 | |
| dc.contributor.author | Westberry BP | |
| dc.contributor.author | Rio M | |
| dc.contributor.author | Waterland MR | |
| dc.contributor.author | Williams MAK | |
| dc.coverage.spatial | England | |
| dc.date.accessioned | 2024-12-02T22:22:02Z | |
| dc.date.available | 2024-12-02T22:22:02Z | |
| dc.date.issued | 2024-06-01 | |
| dc.description.abstract | It is well established that solutions of both polymeric and oligomeric κ-carrageenan exhibit a clear change in optical rotation (OR), in concert with gel-formation for polymeric samples, as the solution is cooled in the presence of certain ions. The canonical interpretation - that this OR change reflects a 'coil-to-helix transition' in single chains - has seemed unambiguous; the solution- or 'disordered'-state structure has ubiquitously been assumed to be a 'random coil', and the helical nature of carrageenan in the solid-state was settled in the 1970s. However, recent work has found that κ-carrageenan contains substantial helical secondary structure elements in the disordered-state, raising doubts over the validity of this interpretation. To investigate the origins of the OR, density-functional theory calculations were conducted using atomic models of κ-carrageenan oligomers. Changes were found to occur in the predicted OR owing purely to dimerization of chains, and - together with the additional effects of slight changes in conformation that occur when separated helical chains form double-helices - the predicted OR changes are qualitatively consistent with experimental results. These findings contribute to a growing body of evidence that the carrageenan 'disorder-to-order' transition is a cooperative process, and have further implications for the interpretation of OR changes demonstrated by macromolecules in general. | |
| dc.description.confidential | false | |
| dc.edition.edition | June 2024 | |
| dc.format.pagination | 121975- | |
| dc.identifier.author-url | https://www.ncbi.nlm.nih.gov/pubmed/38494229 | |
| dc.identifier.citation | Westberry BP, Rio M, Waterland MR, Williams MAK. (2024). On the origin of optical rotation changes during the κ-carrageenan disorder-to-order transition.. Carbohydr Polym. 333. (pp. 121975-). | |
| dc.identifier.doi | 10.1016/j.carbpol.2024.121975 | |
| dc.identifier.eissn | 1879-1344 | |
| dc.identifier.elements-type | journal-article | |
| dc.identifier.issn | 0144-8617 | |
| dc.identifier.number | 121975 | |
| dc.identifier.pii | S0144-8617(24)00201-7 | |
| dc.identifier.uri | https://mro.massey.ac.nz/handle/10179/72152 | |
| dc.language | eng | |
| dc.publisher | Elsevier Ltd. | |
| dc.publisher.uri | https://www.sciencedirect.com/science/article/pii/S0144861724002017 | |
| dc.relation.isPartOf | Carbohydr Polym | |
| dc.rights | (c) 2024 The Author/s | |
| dc.rights | CC BY 4.0 | |
| dc.rights.uri | https://creativecommons.org/licenses/by/4.0/ | |
| dc.subject | Carrageenan | |
| dc.subject | Density-functional theory | |
| dc.subject | Machine learning | |
| dc.subject | Molecular dynamics | |
| dc.subject | Optical rotation | |
| dc.title | On the origin of optical rotation changes during the κ-carrageenan disorder-to-order transition | |
| dc.type | Journal article | |
| pubs.elements-id | 487547 | |
| pubs.organisational-group | Other |